Polar Effects. Part 14. Inductive Charge Dispersal in Bicyclo[2.2.2]oct-1-yl Cations

The rate constants (log k) for solvolysis of 2‐, 3‐, and 4‐substituted bicyclo[2.2.2]octyl p‐nitrobenzenesulfonates 10, 11 and 12, respectively, correlate linearly with the corresponding inductive substituent constants s̀ Iq. The formation of the ion pairs 9 is, therefore, controlled by the I effect of neighboring substituents. It follows from the corresponding reaction constants ρ1 of −1.54, −1.12, and −1.22 that inductivity is highest at the positions α to C(1). It is lower and practically equal at the β‐ and γ‐positions. Therefore, charge dispersal is similar to that previously observed in the quinuclidinium ion 7.